CN102947343A - Manufacturing of microcellulose - Google Patents
Manufacturing of microcellulose Download PDFInfo
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- CN102947343A CN102947343A CN2011800280416A CN201180028041A CN102947343A CN 102947343 A CN102947343 A CN 102947343A CN 2011800280416 A CN2011800280416 A CN 2011800280416A CN 201180028041 A CN201180028041 A CN 201180028041A CN 102947343 A CN102947343 A CN 102947343A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
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Abstract
The present invention relates to a process for producing microcellulose comprising a) acidifying fibrous cellulosic material, b) washing the acidified cellulosic material, c) optionally dewatering the washed cellulosic material, and d) hydrolyzing the washed or washed and dewatered cellulosic material under acidic conditions at a temperature of at least 120 DEG C and at a consistency of at least 8% on dry weight of the cellulose.
Description
Invention field
The present invention relates to be prepared by fibrous cellulosic materials the method for Microcrystalline Cellulose, the method comprises acidification step and hydrolysing step.
Background of invention
Microcrystalline Cellulose (being also referred to as the Mierocrystalline cellulose and the avicel cellulose that for example reach equilibrium polymerization degree (Level-off DP)) is the universal product in food, medicine, makeup, paper and cardboard and many other application for example in many industrial application.Microcrystalline Cellulose also can be used for producing the derivative of Microcrystalline Cellulose, for example prezenta, CMC, nano-cellulose and various composite prod.
Some methods for the production of Microcrystalline Cellulose have been proposed in patent documentation.
US 2978446 has described the Mierocrystalline cellulose that reaches equilibrium polymerization degree (DP, degree of polymerization) by acid hydrolysis and mechanical treatment production.Utilization is boiled in 2.5 nominal hydrochloric acid (HCl) and is made cellulose hydrolysis.Therefore acid concentration is 9%, and temperature is approximately 105 ℃.Do not stipulate the concentration of paper pulp and the amount of add of acid.The Mierocrystalline cellulose of hydrolysis need to be in aqueous medium mechanical depolymerization.
US 3278519 has described by making cellulose hydrolysis production reach the cellulosic similar approach of equilibrium polymerization degree with 2.5 nominal HCl or under 250 °F (121 ℃) with 0.5%HCl under 105 ℃.Do not stipulate the concentration of paper pulp and the amount of add of acid.
US 3954727 discloses by making cellulose hydrolysis produce the method for avicel cellulose with dilute sulphuric acid under 120-160 ℃ temperature.Mierocrystalline cellulose is joined wherein dilute sulphuric acid to have 1% concentration and Mierocrystalline cellulose-acid substance and has 5% concentration.Therefore, the concentration of paper pulp is low and high based on the amount of the acid of Mierocrystalline cellulose dry weight basis.
US 7037405 has described a kind of method, former paper pulp material contact with acid and heats under the temperature that improves and then carries out mechanical treatment.The suitable acid concentration of mentioning is the 1-5% of mixture, and suitable pulp density is 3-50%, and suitable temperature range is 80-120 ℃, and the suitable reaction times is 30 minutes-4 hours.After acid hydrolysis, pulp mixture is carried out mechanical treatment so that the fiber depolymerization.Preferably, the mechanical depolymerization treatment step cuts into the approximately micron size of 1-10 micron-scale with the crystalline fibers crude granule.The method of US 7037405 is subjected to complicated production technique.After acid hydrolysis, need the mechanical depolymerization step.Should the stage need the correct grinding unit of high cost and the correct grinding energy of 5-100kWh/ ton aborning.
US 6228213 discloses by acid solution being joined in the Mierocrystalline cellulose and with Mierocrystalline cellulose and acid solution and has fed the method for producing avicel cellulose by forcing machine, wherein makes described Mierocrystalline cellulose stand acid hydrolysis and forms avicel cellulose.The temperature of extruder barrel is 80-200 ℃ during being hydrolyzed.Because the pressure that the temperature of forcing machine and the die head of forcing machine or screw rod produce, Mierocrystalline cellulose is melting in forcing machine, and this allows to carry out closer contact between Mierocrystalline cellulose and the acid.The compression ratio of extruder screw is 1.5:1 and 3:1, preferred approximately 3:1.The shortcoming of forcing machine is their costlinesses, and maintenance cost is quite high, and the mechanical energy input that they need to be high, by being estimated as at least 100kWh of dried fibres element per ton, except typically the 150kWh(heat energy is inputted at least).
US 5543511 has described at the 100-200 ℃ of lower Mierocrystalline cellulose that reaches the equilibrium polymerization degree with oxygen and/or carbonic acid gas use partial hydrolysis production.
US 4427778 has described the Mierocrystalline cellulose that reaches the equilibrium polymerization degree by enzymic hydrolysis production.
In view of above-mentioned method for the production of Microcrystalline Cellulose, exist to produce Microcrystalline Cellulose in addition the needs of the method for efficient and cost-effective more.
Summary of the invention
According to the present invention, find that unexpectedly the high-quality Microcrystalline Cellulose with narrow size distribution can be produced by the following method by fibrous cellulosic materials: at first with the fibrous cellulosic materials acidifying, then wash the cellulose materials of this acidifying, make at last the cellulosic material hydrolysis of this washing.Size distribution can easily be controlled by the condition that changes acidification step and hydrolysing step.
Accompanying drawing is briefly described
Fig. 1 has shown the grain size distribution curve of Microcrystalline Cellulose produced according to the invention under the hydrolysis time of 165 ℃ hydrolysis temperature and 180 minutes, and
Fig. 2 has shown the grain size distribution curve of Microcrystalline Cellulose produced according to the invention under the hydrolysis time of 150 ℃ hydrolysis temperature and 120 minutes
Detailed Description Of The Invention
According to the invention provides the method for producing Microcrystalline Cellulose, the method comprises:
A) with the fibrous cellulosic materials acidifying,
B) wash the cellulose materials of this acidifying,
C) the cellulose materials dehydration that randomly will wash, and
D) with at least 120 ℃ temperature with at least 8% concentration of pressing the Mierocrystalline cellulose dry weight basis, under acidic conditions, make the cellulosic material hydrolysis of this washing or washing and dehydration.
The term that uses in this specification sheets " Microcrystalline Cellulose " comprises avicel cellulose MCC, but also refers to imperfect crystal but can contain the similar product in some amorphous territories.Microcrystalline Cellulose of the present invention typically has approximately 0-15 % by weight, preferred 0-10 % by weight, more preferably 0.5-7 % by weight, the hemicellulose level of 1-5% weight most preferably, described content records by typical carbohydrate analysis method (Determination of hemicelluloses and pectins in wood and pulp fibres by acid methanolysis and gas chromatography.1996.Nordic pulp and paper research journal nro 4,1996.216-219 page or leaf).
The present invention is based on such discovery: the cellulosic fibre of having removed metal becomes acidity, and this acidity is enough to keep (sustain) automatic hydrolysis, wherein utilizes the own acidity of cellulosic fibre.Cellulosic fibre contains the acidic-group that is attached to fibre wall, for example the ionogen of uronic acid and xylogen institute combination.During fiber contains usually and the metal ion of fiber acidity, for example Na
+, Ca
2+, Mg
2+And Mn
2+According to the present invention, remove metal by acidifying and washing from fiber.As the result of this ion exchange treatment, metal removed from fiber and fibre wall ionogen by protonated.For monovalent ion, ion-exchange can be described as follows usually:
Fiber-acid (-) Me
+→ fiber-acid (H)
For divalent-metal ion, ion-exchange can be described as usually:
2[fiber-acid (-)] Me
2+→ 2[fiber-acid (H)]
As the result of this ion-exchange, fiber (being the cell walls of fiber) becomes acidity, and this acidity is enough to keep automatic hydrolysis.The gained hydrolysed mix contains Microcrystalline Cellulose and comes from the reaction product of fiber, and non-metallic ion and salt, this is so that the further processing of Microcrystalline Cellulose is comparatively easy.
Acidification step a) in, preferably cellulose materials is acidified to 4 or be lower than 4, more preferably 3 or be lower than 3 pH value.This pH be preferably 0 or surpass 0, more preferably 0.5 or surpass 0.5, also more preferably 1 or surpass 1.This pH is preferably 0.5-4, more preferably 1-3, most preferably 1.5-2.5.
Acidification step a) in, the pKa value preferably than the acidic-group of cellulosic fibre for example uronic acid and the pKa value that is bonded to the ionogen of xylogen hang down at least 1, preferably at least 1.5, more preferably at least 2 units.
The suitable acid that is used for acidification step is mineral acid, for example sulfuric acid, hydrochloric acid, nitric acid, sodium pyrosulfate or sodium bisulfite.Can also use two or more the mixture in these acid.Preferred mineral acid is sulfuric acid.Can also use organic acid, for example formic acid.
The concentration of cellulose materials is preferably 5-40% with the cellulose materials dry weight basis in the acidification step, more preferably 10-30%.
Temperature in the acidification step is preferably less than 120 ℃, and more preferably 10-90 ℃, most preferably 20-70 ℃.
The residence time in the acidification step is preferably 10-90 minute, more preferably 15-60 minute.
After acidifying, the cellulose materials of acidifying is washed and chooses wantonly dehydration.Washing is preferably undertaken by following: make the cellulose materials of acidifying dewater to remove excessive acid, then dilute the cellulose materials of this dehydration and and then make this material dehydration.Described washing procedure can repeat once or twice.Cellulose materials with washing is diluted to aimed concn at last.
Washing can be undertaken by the industrial pulp washing device that utilization is generally used for the pulp mill machine.Preferred embodiment is included in carries out acidifying in the container, then remove disacidify by screw extruding, follows dilute with water, and again dewaters.
Provide as mentioned, in hydrolysis, utilize the own acidity of cellulose materials.And nonessential acid is joined in the hydrolysing step therefore.Yet, can be with a small amount of based on the Mierocrystalline cellulose dry weight basis, preferred maximum 0.5%, more preferably maximum 0.2%, most preferably maximum 0.18% acid joins in the hydrolysis.
Hydrolysis temperature is preferably 120-185 ℃, and more preferably 150-180 ℃, most preferably 155-175 ℃.
The concentration of cellulose materials is preferably 8-60% with the Mierocrystalline cellulose dry weight basis during being hydrolyzed, more preferably 10-50%, even more preferably 15-50%, most preferably 20-45%.
Hydrolysis time is preferably 20-300 minute, and more preferably 30-240 minute, also more preferably 60-240 minute, most preferably 60-240 minute.
Preferably, hydrolysis is in the situation that carrying out in very large (essential) compression not in the reactor, and the compression ratio of reactor preferably is lower than 1.5:1, more preferably less than 1.2:1.Preferably, during being hydrolyzed, provide mechanical energy input to guarantee uniform chemical substance and temperature distribution and do not have the very great machinery cutting of cellulose matrix to separate with mechanical fiber.
After hydrolysis, if necessary, the Microcrystalline Cellulose-hydrolysate admixture that obtains can neutralize or Microcrystalline Cellulose can be separated with hydrolysate.The Microcrystalline Cellulose that separates can be washed and Microcrystalline Cellulose that separate or washing can be neutralized.Can also the neutralizing acid hydrolysate.Can example such as yellow soda ash, sodium bicarbonate, potassium hydroxide, magnesium hydroxide or sodium hydroxide neutralize.Hydrolysate is rich in the hydrolysis of hemicellulose product, xylose and glucose for example, and can be for the production of ethanol.
Observe, by this specification sheets after a while the median size of described program determination be about 8-100 μ m, the microcrystalline cellulose cellulosic material of preferred 10-60 μ m, can be produced by the following method by fibrous cellulosic materials: acidifying fibrous cellulosic materials at first, then wash the cellulose materials of this acidifying, make at last the cellulosic material hydrolysis of this washing and subsequently depolymerization step not.Key character of the present invention is the high density of cellulose materials in the hydrolysis, and it is preferably at least 20% with the Mierocrystalline cellulose dry weight basis.High density has improved the concentration of chemical substance, and this has Beneficial Effect to speed of response, and so that easier from reaction mixture recovery Microcrystalline Cellulose.In addition, adding heat request can be lower.
Fibrous cellulosic materials as parent material can be any cellulose materials that can be hydrolyzed under prescribed condition in the methods of the invention.Fibrous cellulosic materials is also nonessential to be the pure cellulose material, but it also can contain for example xylogen of other material.
It is maximum 5% that the content of lignin of fibrous cellulose parent material is preferably, more preferably maximum 2%, and most preferably maximum 1%.
The fibrous cellulose parent material typically has approximately 3-15 % by weight, the hemicellulose level of preferred 5-10 % by weight, described content records by typical carbohydrate analysis method (Determination of hemicelluloses and pectins in wood and pulp fibres by acid methanolysis and gas chromatography.1996.Nordic pulp and paper research journal nro 4,1996.216-219 page or leaf).
The staple length of fibrous cellulose raw material is preferably 5-0.2mm.For non-wood fiber shape cellulose materials, cotton for example, staple length can be greater than 5mm.
Fibrous cellulosic materials can derive from the xylophyta material, for example soft wood or hardwood.
Preferred fibrous cellulosic materials is bleaching or unbleached dissolving pulp, for example sulfate pulping, soda-AQ paper pulp, sulfite pulp, neutral sulfite pulp, acid accumulator sulfite paper pulp or organic solvent paper pulp.Paper pulp can be softwood pulp or bardwood pulp.Paper pulp can be the paper pulp that obtains immediately after the boiling or after boiling the paper pulp of delignification or the paper pulp of delignification and bleaching.The paper pulp of preferred delignification is O
2The paper pulp of delignification.Preferred paper pulp is the paper pulp of full bleaching.
Also can use according to the present invention and to derive from for example fibrous cellulosic materials of stalk, flax, hemp, sisal hemp, abaca or the bamboo of cotton, grass, bagasse, cereal crop of non-woody lignocellulosic plants material.Usually with these vegetable materials of alkaline matter for processing ligno-cellulosic materials is broken to Mierocrystalline cellulose, xylogen and hemicellulose, then go out Mierocrystalline cellulose from described mixture separation.The vegetable material of some poor xylogen, for example velveteen or cotton fabric are not to necessarily require to process with alkaline matter.Rear kind of material can contain the fibrous material that has greater than 90% cotton fiber.
Fibrous cellulosic materials, for example dissolving pulp preferably have be lower than 40 Kappa numbers, more preferably less than 30 Kappa numbers, most preferably be lower than the content of lignin of 10 Kappa numbers.
According to the preferred embodiments of the invention, the Microcrystalline Cellulose of producing has narrow size distribution, wherein median size (D50) is 10-60 μ m, and preferably size distribution (D90) is so that the particle of at least 90 volume % has the size that is lower than 250 μ m.Particle diameter by this specification sheets after a while described program measure, described program comprises the supersound process that may cause sample depolymerization (deagglomerization) or decompose (disintegration).
The microcrystalline cellulose cellulosic material that obtains by the inventive method typically has in without any the mechanical treatment situation by this specification sheets 8-100 μ m of described program determination after a while, the median size of preferred 10-60 μ m.If need thinner particle diameter, but the described structure of refinement then.Therefore, can (if necessary) pass through to use suitable device, for example the rubbing device microcrystalline cellulose cellulosic material that will derive from hydrolysis is refined as less particle diameter, and wherein said refinement realizes by grinding stone (for example Masuko mill), high-shear mixer or jet milled machine.
The purity that a benefit of the inventive method is final Microcrystalline Cellulose is appropriate high and product can easily wash to remove low-molecular-weight carbohydrate.Through the Mierocrystalline cellulose purity of the Microcrystalline Cellulose of washing even can surpass 97%.
The yield of Microcrystalline Cellulose depends on processing condition, for example temperature, the amount of acid and the residence time and the concentration of acidifying and hydrolysis.Typical yield is at least 80%, preferably at least 85%, and yield even can be 90% or higher.
According to the present invention, Microcrystalline Cellulose can be produced in any suitable equipment (for example being equipped with the container of mixing tank or screw rod conveyor) that Mierocrystalline cellulose-acid mixture is not carried out therein any very large (substantial) compression.The latter can be the M ﹠amp with screw rod conveyor; The device of D pulp digester type.Other device can be continuous bleaching reactor or downflow system continuous steamer, for example pulp digester of Kamyr type.Compression ratio (if any) typically is lower than 1.5:1, more preferably less than 1.2:1.
Experimental section
Following examples have been described the operation of Microcrystalline Cellulose produced according to the invention.
In the 5L pulp digester that stirs with the mixing tank that passes lid, carry out the boiling experiment.Pulp digester is used in around the oil that flows in the chuck of this pulp digester and heats.Turning oil electricity consumption in independent unit is heated.
All boiling experiments are all undertaken by following mode.The cellulose materials that 300g is calculated by self dry weight (owen dry), namely paper pulp or other carry out depolymerization according to SCAN C 18:65, and dehydration is to 35% concentration in spin drier.Then with deionized water this paper pulp is diluted to 10% concentration and uses sulfuric acid (H
2SO
4) with pH regulator to 2.At room temperature kept this slurry 30 minutes.Thereafter with this pulp suspension Rotary drying to about 35% concentration to remove excessive acid.With deionized water by this paper pulp of following washing: at first it is diluted to 10% concentration and then with its Rotary drying to about 35% concentration.The repeated washing operation.Then with deionized water with this paper pulp redilution to aimed concn and transfer to autoclave for hydrolysis stage.Rate of heating with 2 ℃/min is heated to temperature of reaction until reach the goal response temperature with autoclave from room temperature.Therefore for example be heated to 150 ℃ of costs 65 minutes, be heated to 165 ℃ of costs 72.5 minutes.When reaching the goal response temperature, cooking time begins.During whole cooking time, make temperature remain in target temperature value.When cooking time is finished, by cooling off this autoclave unit with cold water (approximately 10 ℃ of temperature) refrigeration cycle oil.The cooling of reactor spends approximately 20 minutes.
Open the autoclave unit of cooling and cellulose mixtures shifted out and in the sack of being made by the cloth with 40 μ m holes (silk cloth), wash.For washing, use the 6000ml deionized water.
The particle diameter of cellulose product is by making with Mastersizer 2000(Ma Erwen (Malvern) the Instruments Ltd that is equipped with wetting dispersal unit Hydro 2000MU) measure with laser diffraction.Measure according to following operation:
With the cellulose materials sample dispersion in 500ml distilled water.Regulate sample concentration take degree of haze (obscuration) as 10% mode.Pump/the stirring velocity of dispersal unit is adjusted to 1500rpm.Before grain diameter measurement, sample is used supersound process 60 seconds.Measured particle diameter by 60 second timed interval with 3 continuously measureds.Calculate the mean value of 3 observed values.Each background value of measuring before sample.The Measuring Time that is used for each background and each sample measurement value is 5 seconds.Use the Fraunhofer parameter to measure.At Master sizer 2000application note MRK 561 (Wet method development for laser diffraction measurements) by Malvern Instruments and ISO-13320-1 (1:1999), provide the additional information about the laser diffraction measurement principle among the Particle size analysis – Laser diffraction General Principles.
With above-mentioned experiment processes employ in the paper pulp of full bleaching.The concentration of hydrolysis stage is 15%, and boiling temperature is 165 ℃, and cooking time is 180 minutes.The size distribution that in Fig. 1, has shown the Microcrystalline Cellulose that obtains.
This experimental result shows, in the situation that do not add acid in 165 ℃ of lower hydrolysis 180 minutes, is the even crystallite Mierocrystalline cellulose of the better quality of approximately 20 μ m in the situation that obtain median size without any mechanical treatment.
Embodiment 2
With above-mentioned experiment processes employ in the paper pulp of full bleaching.The concentration of hydrolysis stage is 15%, and boiling temperature is 150 ℃, and cooking time is 120 minutes.The size distribution that in Fig. 2, has shown the Microcrystalline Cellulose that obtains.
This experimental result shows, in the situation that do not add acid in 150 ℃ of lower hydrolysis 120 minutes, is the even crystallite Mierocrystalline cellulose of the suitable better quality of approximately 50 μ m in the situation that obtain median size without any mechanical treatment.Compare with embodiment 1, particle diameter is larger a little.
Claims (14)
1. method of producing Microcrystalline Cellulose, the method comprises:
A) with the fibrous cellulosic materials acidifying,
B) wash the cellulose materials of this acidifying,
C) the cellulose materials dehydration that randomly will wash, and
D) with at least 120 ℃ temperature with at least 8% concentration of pressing the Mierocrystalline cellulose dry weight basis, under acidic conditions, make the cellulosic material hydrolysis of this washing or washing and dehydration.
2. according to claim 1 method, wherein described cellulose materials is acidified to 4 or be lower than 4, preferred 3 or be lower than 3, the more preferably pH value of 1.5-2.5.
3. according to claim 1 and 2 method is wherein used mineral acid, and preferably sulfuric acid, hydrochloric acid, nitric acid, sodium pyrosulfate or sodium pyrosulfate are with described fibrous cellulosic materials acidifying.
4. each method according to claim 1-3, wherein the temperature in the acidification step is preferably 10-90 ℃ less than 120 ℃, more preferably 20-70 ℃.
5. each method according to claim 1-4, wherein acidificatoin time is 10-90 minute, preferred 15-60 minute.
6. each method according to claim 1-5 is wherein utilized the own acidity of described cellulose materials in hydrolysis.
7. each method according to claim 1-6, wherein the temperature in the steps d is 120-185 ℃, preferred 150-180 ℃, more preferably 155-175 ℃.
8. each method according to claim 1-7, wherein the concentration of cellulose materials described in the steps d is counted 8-60% with the Mierocrystalline cellulose dry weight, preferred 10-50%, more preferably 15-50%, most preferably 20-45%.
9. each method according to claim 1-8, wherein hydrolysis time is 20-300 minute, preferred 30-240 minute, more preferably 60-240 minute.
10. each method according to claim 1-9, wherein said fibrous cellulosic materials derives from the xylophyta material, for example soft wood or hardwood.
11. each method according to claim 1-10, wherein said fibrous cellulosic materials comprises bleaching or unbleached dissolving pulp, for example sulfate pulping, soda-AQ paper pulp, sulfite pulp, neutral sulfite pulp, acid accumulator sulfite paper pulp or organic solvent paper pulp.
12. each method according to claim 1-11, wherein said fibrous cellulosic materials derives from nonwood plant materials, for example the stalk of cotton, grass, bagasse, cereal crop, flax, hemp, sisal hemp, abaca or bamboo.
13. each method according to claim 1-12, wherein said fibrous cellulosic materials for example dissolving pulp have and are lower than 40 Kappa numbers, preferably are lower than 30 Kappa numbers, more preferably less than the content of lignin of 10 Kappa numbers.
14. each method according to claim 1-13, the Microcrystalline Cellulose of wherein producing has the median size of 10-60 μ m, and preferably size distribution so that the particle of at least 90 volume % has the size that is lower than 250 μ m.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI20105639A FI123270B2 (en) | 2010-06-07 | 2010-06-07 | Manufacturing of microcellulose |
| FI20105639 | 2010-06-07 | ||
| PCT/FI2011/050523 WO2011154597A1 (en) | 2010-06-07 | 2011-06-06 | Manufacturing of microcellulose |
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|---|---|
| CN102947343A true CN102947343A (en) | 2013-02-27 |
| CN102947343B CN102947343B (en) | 2016-03-30 |
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| CN201180028041.6A Active CN102947343B (en) | 2010-06-07 | 2011-06-06 | The manufacture of Microcrystalline Cellulose |
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| Country | Link |
|---|---|
| US (1) | US9587038B2 (en) |
| EP (1) | EP2576627B1 (en) |
| CN (1) | CN102947343B (en) |
| BR (1) | BR112012031247B1 (en) |
| CA (1) | CA2801986C (en) |
| FI (1) | FI123270B2 (en) |
| PL (1) | PL2576627T3 (en) |
| RU (1) | RU2570675C2 (en) |
| UY (1) | UY33436A (en) |
| WO (1) | WO2011154597A1 (en) |
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| CN106519173A (en) * | 2016-11-29 | 2017-03-22 | 桂林理工大学 | Method for preparing shape memory polyurethane from hyperbranched modified sisal microcrystals |
| CN107936125A (en) * | 2017-12-11 | 2018-04-20 | 厦门大学 | A kind of preparation method of micro-nano cellulose |
| CN111019154A (en) * | 2019-12-30 | 2020-04-17 | 上海昶法新材料有限公司 | Method for extracting lignin and microcrystalline cellulose from chemi-mechanical pulp treatment waste liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2505545C1 (en) * | 2012-07-31 | 2014-01-27 | Закрытое акционерное общество "Инновационный центр "Бирюч" (ЗАО "ИЦ "Бирюч") | Method for obtaining nano-cellulose |
| CN102911274B (en) * | 2012-10-17 | 2014-05-28 | 浙江理工大学 | Method for chemically preparing nano microcrystalline cellulose by utilizing moso bamboo |
| SE1350057A1 (en) * | 2013-01-18 | 2014-07-19 | Process for manufacturing microfibrillated cellulose from a precursor material | |
| FI129421B (en) * | 2014-03-12 | 2022-02-15 | Maelkki Yrjoe | Production and use of nanocellulose and its precursors |
| US10597820B2 (en) * | 2015-05-14 | 2020-03-24 | DuPont Nutrition USA, Inc. | Method of making bleached microcrystalline cellulose |
| FI130254B (en) * | 2016-02-03 | 2023-05-11 | Kemira Oyj | A process for producing microfibrillated cellulose and a product thereof |
| US10287366B2 (en) | 2017-02-15 | 2019-05-14 | Cp Kelco Aps | Methods of producing activated pectin-containing biomass compositions |
| BG67355B1 (en) * | 2017-11-17 | 2021-07-15 | Свилоза - Ад | Method for preparing microcrystalline cellulose |
| FI129209B (en) * | 2018-02-07 | 2021-09-15 | Andritz Oy | Process for producing microcrystalline cellulose |
| RU2684082C1 (en) * | 2018-04-11 | 2019-04-03 | Общество С Ограниченной Ответственностью "Национальная Исследовательская Компания" | Method for producing microcrystalline cellulose |
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- 2011-06-06 CN CN201180028041.6A patent/CN102947343B/en active Active
- 2011-06-06 PL PL11729639T patent/PL2576627T3/en unknown
- 2011-06-06 UY UY0001033436A patent/UY33436A/en active IP Right Grant
- 2011-06-06 RU RU2012155800/05A patent/RU2570675C2/en active
- 2011-06-06 EP EP11729639.2A patent/EP2576627B1/en active Active
- 2011-06-06 CA CA2801986A patent/CA2801986C/en active Active
- 2011-06-06 WO PCT/FI2011/050523 patent/WO2011154597A1/en active Application Filing
- 2011-06-06 US US13/697,729 patent/US9587038B2/en active Active
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519173A (en) * | 2016-11-29 | 2017-03-22 | 桂林理工大学 | Method for preparing shape memory polyurethane from hyperbranched modified sisal microcrystals |
| CN107936125A (en) * | 2017-12-11 | 2018-04-20 | 厦门大学 | A kind of preparation method of micro-nano cellulose |
| CN111019154A (en) * | 2019-12-30 | 2020-04-17 | 上海昶法新材料有限公司 | Method for extracting lignin and microcrystalline cellulose from chemi-mechanical pulp treatment waste liquid |
Also Published As
| Publication number | Publication date |
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| CA2801986C (en) | 2017-08-15 |
| US9587038B2 (en) | 2017-03-07 |
| EP2576627A1 (en) | 2013-04-10 |
| UY33436A (en) | 2011-12-30 |
| EP2576627B1 (en) | 2018-08-08 |
| PL2576627T3 (en) | 2019-01-31 |
| FI123270B2 (en) | 2019-04-15 |
| BR112012031247B1 (en) | 2020-05-26 |
| CN102947343B (en) | 2016-03-30 |
| CA2801986A1 (en) | 2011-12-15 |
| FI20105639L (en) | 2011-12-08 |
| FI20105639A0 (en) | 2010-06-07 |
| RU2570675C2 (en) | 2015-12-10 |
| FI20105639A (en) | 2011-12-08 |
| BR112012031247A2 (en) | 2018-03-06 |
| RU2012155800A (en) | 2014-07-20 |
| US20140179912A1 (en) | 2014-06-26 |
| WO2011154597A1 (en) | 2011-12-15 |
| FI123270B (en) | 2013-01-31 |
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